Composition of matter



atented June 29, 1948 COMPOSITION OF MATTER Charles M. Blair, Jr.,Webster Groves, Mo., as-

signor to Petrolite Corporation, Ltd., Wilmington, Del., a corporationof Delaware No Drawing. Original application December 31,

1943, Serial No. 516,538. Divided and this application September 12,1945, Serial No. 615,913

Claims. 1

The present invention relates to a new class of chemical substances andmore particularly to new reagents which are useful as lubricating oiladditives, rust preventive compounds and for other purposes hereinafterdescribed. This application is a division of abandoned applicationSerial No. 516,536, filed December 31, 1943, which is in turn acontinuation-in-part of my earlier application Serial No. 461,035, filedOctober 6, 1942, now Patent No. 2,342,113, February 22, 1944.

Briefly, this new class of chemical compounds may be described asconsisting of esters derived by an estcrification reaction between ahigh molecular weight alcohol and a polybasic carboxy acid or anhydrideof the kind hereinafter described.

The alcohols contemplated as reactants in preparing the presentcompounds are the high molecular weight alkyl, aralkyl, and alicyclicalcohols in which there is present at least one alkyl residue containingat least eight and not more than thirty-two carbon atoms.

The polybasic acids or anhydrides contemplated as reactants iorproduction of this new class of compounds are obtained by thecondensation of an alpha-beta ethylenic carboxy acid or anhydride withan unsaturated, nonhydroxylated fatty acid containing from ten totwenty-four carbon atoms in its carbon chain. The desired polybasic acidor anhydride reactants may be prepared by two different types ofreaction. one type of reaction involves the condensation of an alphabetaethylenic acid or anhydride with a conjugated, unsaturated,nonhydroxylated fatty acid. The second type of reaction involves thecondensation of an alpha-beta ethylenic acid or anhydride with a,non-conjugated, unsaturated, nonhydroxylated fatty acid.

It is well known that maleic anhydride and other alpha-beta ethyienicacids or anhydrides will condense with conjugated, unsaturated fattyacids in accordance with Thiele's theory of 1-4 addition. The fatty acidin this case, of course, must contain at least two carbon-to-carbondouble bonds and these must be conjugated. This type of reaction hasbeen thoroughly studied by Diels and coworkers, and is often referred toas the Diels diene synthesis. The products are often called dienesynthesis adducts.

Examples of suitable fatty acids which will take part in a Dielscondensation include: Geranic acid, elaeostearic acid, 10,12-octadecadienoic acid, tung oil fatty acids, etc. Actually, the estersof these acids, such as the triglycerides or the esters of mono-, di-,or other polyhydric alcohols may be employed in this condensation inplace of the fatty acid itself. Examples of suitable esters include:methyl-l0, 12-octadecadienoate, lycoldielaeostearate, oitacica oil, tungoil, dehydrated conjugated castor oil, ethyl dehydrogeranate and thelike.

The alpha-beta ethylenic carboxy acids or anhydrides which are suitablefor use in the aforementioned Diels diene synthesis for preparation ofthe present products are those containing less than ten carbon atoms andare exemplified by crotonic acid, maleic acid, fumaric acid, citraconicacid, glutaconic acid, acrylic acid, maleic anhydride, and citraconicanhydride.

Polybasic acids or anhydrides contemplated as reactants for productionof this new class of compounds are also obtained by the condensation ofan alpha-beta ethylenic acid, or anhydride with an unsaturated,non-conjugated, non-hydroxylated fatty acid containing from ten totwentyfour carbon atoms in the carbon chain. It has recently been shownby Clocker, U. S. Patents 2,188,882 to 2,188,892 inclusive, and Bickfordet al., Oil and Soap, February, 1942, page 23 et seq., that suchcondensations may be brought about by heating the reactants at asuitable elevated temperature, usually above 200 C. and sometimes attemperatures above 300 C. The products formed are also acids oranhydrides, since the reaction appears not to involve the destruction ofthese groups. The alpha-beta ethylenic acids or anhydrides which aresuitable for use in the aforementioned condensation with non-conjugated,unsaturated, non-hydroxylated fatty acids are those containing less thanten carbon atoms and are exemplified by crotonic acid, maleic acid,fumaric acid, citraconic acid. glutaconic acid, acrylic acid, maleicanhydride, and citraconic anhydride. Reference herein and in the claimsto alpha-beta unsaturated acids is intended to include the anhydridescorresponding to such acids. Actually they are recognized as beingfunctionally equivalent in condensations of the kinds hereincontemplated.

Suitable non-conjugated, unsaturated, nonhydroxylated fatty'acids foruse in condensation reactions with the above-mentioned alpha-betaethylenic acids are those containing from ten to twenty-four carbonatoms in their carbon chains, and include undecylenic acid, oleic acid,elaidic acid, linoleic acid, linolenic acid, etc.

For the production of the present compositions using as one reactant theabove described condensation compounds of Clocker, I usually prefer toemploy a condensation product derived from amazes a glyceridecontaining, in esterified form, a large proportion of non-conjugated,unsaturated, nonhydroxylated fatty acid. Examples of such glycerides areolive 011. corn oil, cottonseed oil, linseed oil, rapeseed oil, perillaoil, cranberry seed oil, menhaden oil, cod oil, whale oil, heat bodiedlinseed oil, etc.

When glycerides or other esters of the nonconiugated, unsaturated,non-hydroxylated fatty acids are employed in the condensation reaction,the final product is not necessarily a polybasic acid or anhydride,since a monocarboxy, alphabeta ethylenic acid, such as crotonic acid,may have been employed in the condensation. However, such monobasic acidcondensation products are contemplated as reactants in preparing my newcompositions; and they are intended to be included when reference ismade to a polybasic carboxy acid or anhydride reactant. Actually theyare the partial esters of dibasic acids and under certain conditions mayfunction as polybasic acids by interchange of the alcohol residue with ahydroxyl-containing reactant.

My new compositions may be prepared by an esterification reactionbetween a diene synthesis adduct or a Clocker adduct and a highmolecular weight alcohol. The alcohols contemplated are those containingan alkyl group of from eight to thirty-two carbon atoms, but in additionmay contain other hydrocarbon groups or residues such as aromatic rings,alicyclic rings or even heterocyclic rings. The hydroxyl group may beattached either to the alkyl residue or to the nonalkyl portion of themolecule. but of course must be capable of forming an ester by reactionwith the Clocker adduct. These alcohols may be either straight or branchchains and may be either primary, secondary, or tertiary, but arepreferably primary or secondary, as such alcohols generally are moreeasily reacted with a minimum of side reactions to form the desiredesters. Examples of suitable alcohol reactants include the following:n-octyl alcohol, 2-ethyl hexanol, lauryl alcohol, cetyl alcohol,octadecyl alcohol, ceryl alcohol, para-iso-octyl phenol, lauryl alcohol,'l-ethyl-Z-methylundecanol-4, 3.9-diethyl tridecanol-6, dodecyl phenol,decylcyclohexanol, alcohols obtained by reduction of naphthenic acids,alcohols obtained by the hydrolysis of halogenated paraiiin wax,alcohols obtained by the oxidation of high boiling petroleum fractions,and alcohols obtained by the reduction of synthetic acids resulting fromthe oxidation of Pennsylvania lubricating oil fractions.

Other suitable alcohols include the olefinic alcohols containing fromeight to thirty-two carbon 'atoms and alcohols containing an oleflnicresidue of from eight to thirty-two carbon atoms. The presence of adouble bond in the hydrocarbon chain does not appear to alter theusefulness of the effectiveness of the ester products, and for thepurposes of the present invention the term alkyl" as applied indescribing suitable alcohols is intended to include olefinic residueswhich can be considered as being derived from an alkyl residue bydehydrogenation. Suitable olefinic alcohols include oleyl alcohol,undecenyl alcohol, hexadecenyl alcohol, eicosenyl alcohol, cardanol. andthe like.

For convenience in describing the reactions involved in preparing thepresent products, the diene synthesis adducts and the Clocker adductswill be referred to simply as unsaturated fatty acid adducts, and thisterm is also intended to .r a l refer to adducts derived from the estersof the unsaturated fatty acids. In the examples it will be clear whetherthe adduct reactant employed is of the diene synthesis tape or theClocker type. A mixture of the two may be employed, if desired.

In carryingout the synthesis of the present class of compounds, it isusually most convenient to prepare the desired adduct of the unsaturatedfatty acid and an alpha-beta ethylenic acid, after which the desiredhigh molecular weight alcohol is added and esterified by heating andstirring. It is not necessary that all of the carboxyls or potential(anhydride) carboxyls of the adduct be esterified with high molecularweight alcohols, and, as will be discussed hereinafter, some carboxylswilloften be left unesterified.

The following examples illustrate the preparation of some of the presentproducts:

Example 1 A diene synthesis adduct was first prepared by refluxing forfour hours a mixture of one hundred and fifty lbs. of tung oil acids,fifty lbs. of maleic anhydride. one hundred lbs of benzol, and abouttwenty gms. of iodine.

To the above adduct in benzol was added one hundred and eighty-six lbs.of lauryl alcohol and refluxing was continued with a water trap underthe condenser. After two hours refluxing, the benzol and water ofreaction were slowly distilled off, leaving a viscous reddish oil.

Example 2 Tung oil was substituted for the tung oil acids in Example 1.The product in this case was quite soluble in kerosene and lubricatingoil.

Example 3 Forty-two lbs of crotonic acid were substituted for the fiftylbs. of maleic anhydrided in Example 2, and only ninety-three lbs oflauryl alcohol were employed in the esterification step.

Example 4 A Clocker adduct was prepared by heating and stirring under anair condenser a mixture-of three hundred lbs. of linseed oil and twohundred lbs. of citraconic anhydride. The temperature of this mixturewas slowly raised to 230 C. and held at this point for two and one-halfhours.

Fifty lbs. of the above adduct was heated and stirred in an open vesselwith fifty lbs. of ceyl alcohol. The temperature was raised to 240 C.and held for forty-flve minutes. The final product was a viscous oil,clearly soluble in kerosene and in lubricating oil.

Example 5 Maleic anhydride was substituted for the citraconlc anhydrideof Example 4. 4

Example 6 Methyl linolenate was substitued for the linseed oil ofExample 4.

Example 7 Three hundred lbs. or soyabean oil and one hundred lbs. ofmaleic anhydride were heated with stirring under an air condenser. Thetemperature was gradually raised to 240 C. and held at this point forthree hours.

Fifty lbs. of .the above adduct and thirtyfive lbs. of oleyl alcoholwere heated and stirred in an open vessel for one hour at a tem- BAA-4,8

perwture of 250 C. The product was a viscous oil.

Example 8 octylcyclohexanol was substituted ior oleyl alcohol in Example7.

Example 9 Eight hundred and eizhty lbs. of linseed oil and six hundredand seventy-two lbs. or citraconic anhydride were reacted as in Example4 to form an adduct. After cooling the above product, eight hundred andten lbs. of commercial stearyl alcohol were added to the reactionvessel. The temperature was raised to 250 C. and held at that point (orthree hours. A small amount of water was evolved thro h a take-oil.condenser.

Fbr the preparation of rust preventive compounds, various products ofthe above examples may be used directly as such for application to themetal to be protected or may be mixed with a suitable solvent orcarrying agent for application as a slushing oil or grease. Theseproducts may be used alone or in mixtures with other rust preventivereagents. Examples oi such rust preventive compositions are given below:

Roar Psxvamvr Couromms Example A The following reagents were mixed withslight warming until clear and homogeneous:

- Pounds Product of Example 4 100 Monoamyl amine 9 Viscous lubricatingoil (6000 S. U. S. at 100 Mineral spirits 700 This compound is a thin,rust preventive oil suitable for dipping, brushing or spraying.

This product forms thin. adherent, slightly tacky. rust-preventive filmswhich are readily removable in hot water.

Example The product of Example 7 was substituted for the product ofExample in Example B, and the dibutyl amine was omitted.

Example D The following were warmed and stirred until homogeneous; themixture was then filtered to remove the small amount of undissolvedimpurities:

Pounds Product of Example 9 123 Oil soluble petroleum sullonate Viscouslubricating oil 150 Mineral spirits 700 Example E The following weremixed and filtered as in Example D:

Pounds Product of Example 9 180 Cyclohexylamine 8 Petroleum pitchPetrolatum 50 Carbon tetrachloride 600 This product gives a quick dryingfilm of sumclent color to be seen on :the metal surface.

Example F The following were treated as in Example D:

Pounds Product of Example 9 123 Cyclohexylamine 5 Viscous mineral oil(6000 S. U. S. at 100 F.) 250 Kerosene 625 Heavy, grease-like rustpreventives may be prepared by blending the present compounds withpetrola-tum, or mixtures of petrola-tum and other ingredients such asnatural or synthetic resins, rubber, etc.

In some of the examples given above less alcohol has been used in theesteriflcation reaction than corresponds to all of the availablecarboxyls present in the adduct. Any unreacted carboxylic acid oranhydride groups may be left as such or may be neutralized with ammonia,amines, or inorganic bases, in which case the acidic hydrogen isreplaced with an amino, ammonium, or metal ion. Examples B, C, D, E andF above illustrate the use of an amine for neutralizing part of theavailable carboxyl groups of the adduct ester. It is in many instancesunnecessary to neutralize all such free carboxyls and for certain usesthis may be undesirable. In some cases where a rust preventive compoundis to be applied in aqueous solution it is desirable to neutralize thecarboxyl groups of the acidic adduct ester with inorganic bases, ammoniaor low molecular weight amines in order to impart water solubility orwater dispersibility on the reagent.

As pointed out in my above-mentioned Patent No. 2,342,113, the presentcompositions have uses in various other. arts and are there claimedparticularly as additives for lubricating oil.

Products having detergent and sludge dispersing properties may beprepared, for example, by treating the product of Example 4 with calciumhydroxide, to neutralize free carboxy acid groups, heating to completethe reaction and drive off water, dissolving in ligroin, filtering toremove unused calcium hydroxide, and evaporating ligroin from thefiltrate.

Similar products may be prepared from the compounds of the otherexamples where free anhydride or carboxyl groups are present.

If desired, residual carboxy acid groups may be esterified with lowmolecular weight alcohols to yield products with improved oilsolubility.

The present reagents may also be used as break inducers in the Doctorsweetening process, and for such use may be applied as described in U.S. Patent 2,208,505 to Blair and Boydstun.

Residual carboxy acid groups may be reacted with phenols, for example,phenol, catechol, pyrogallol, etc., to yield products with antioxidantproperties. Amino phenols such as paraamino phenol or ortho-amino phenolmay be used either to neutralize carboxyls or to esterify 7 or amidifythem, thus giving compounds of improved antioxidant properties.

Recapitulating, the acidic hydrogens which may remain in the presentclass of chemical reagents-may be left as such or may be replaced by anyequivalent. Such acidic products may be treated with a suitable alkalinematerial such as caustic soda, caustic potash. ammonium hydroxide,calcium hydroxide, magnesium hydroxide, etc., to form the correspondingmetallic salts, or with amines such as amylamine, cyclohexylamine.trlethanolamine, para amino phenol, etc, to form the amine salts. Theacidic hydrogen may be replaced by a lower alcohol residue derived fromalcohols such as ethanol, butanol, hexanol, cyclohexanol, phenol,catechol, etc., to form an ester. Amino alcohols such as theethanolamines. glyceryl amines, etc., may be employed to replace anacidic hydrogen either by esteriflcation or salt formation.

The present class of chemical products appears to have its greatestusefulness in the field of lubricating oil additives and rustpreventives. They are also effective in modifying a crystalline form ofwax, for dispersing sludge accumulations in oil, for increasing oilinessand load bearing capacity of oils and for various other uses. Most ofthese useful properties appear to be related to the surface activity ofthe compounds or their ability to adsorb strongly on metallic or othersurfaces.

It will be obvious to most chemists that various derivatives of thepresent products may be prepared which will have similar properties. Forexample, many of the present products contain carbon-to-carbon doublebonds, either in the fatty acid or alcohol chain, and may be readilysulfurized by heating with sulfur. Such sulfurized derivatives, in someinstances. have valuable properties over and above the originalunsulfurized product. For example, they usually are better antioxidantsand have greater film strength as lubricants.

Other obvious derivatives include those derivable by oxidation, as byblowing with air or oxygen at elevated temperatures, and polymerizedproducts derivable by reacting carboxyl or anhydride containingcompositions with polyhydric alcohols or polyamines.

Having described my invention. I claim:

1. The monohydric alcohol ester of an acidic adduct which is an acyclicalpha-beta unsaturated acid having not over ten carbon atoms, combinedat an intermediate point in the carbon atom chain of a non-hydroxylatedunsaturated fatty acid radical having at least eight and not more thanthirty-two carbon atoms; said radical being an integral part of acompound selected from the class consisting of esters and acids; saidalcohol containing at least one alkyl hydrocarbon radical having atleast eight and not more than thirty-two carbon atoms.

2. The m nohydric alcohol ester of an acidic adduct which is an acyclicpolybasic alpha-beta unsaturated acid having not over ten carbon atoms,combined at an intermediate point in the carbon atom chain of anon-hydroxylated unsaturated fatty acid radical having at least eightand not more than thirty-two carbon atoms; said radical being anintegral part of a compound selected from the class consisting of estersand acids; said alcohol containing at least one alkyl hydrocarbonradical having at least eight and not more than thirty-two carbon atoms.

3. The monohydric alcohol ester of an acidic adduct which is an acyclicpolybasic alpha-beta unsaturated acid having not over ten carbon atoms.combined at an intermediate point in the carbon atom chain of anon-hydrozvlated poly; ethylenic fatty acid radical having at leasteight and not more than thirty-two carbon atoms: said radical being anintegral part of a compound selected from the class consisting of estersand acids; said alcohol containing at least one alkyl hydrocarbonradical having at least eight and not more than thirty-two carbon atoms.a 4. The monohydric alcohol ester of an acidi adduct which is an acyclicpolybasic alpha-beta unsaturated acid having not over ten carbon atoms,combined at an intermediate point in the carbon atom chain of anon-hydroxylated polyethylenic fatty acid radical having eighteen carbonatoms; said radical being an integral part of a compound selected fromthe class consisting of esters and acids; said alcohol containing atleast one alkyl hydrocarbon radical having at least eight and not morethan thirty-two carbon atoms. 5. The monohydric alcohol ester of anacidic adduct which is an acrylic polybasic alpha-beta unsaturated acidhaving not over ten carbon atoms, combined -at an intermediate point inthe carbon atom chain of a non-hydroxylated polyethylenic, vegetablefatty acid radical having eighteen carbon atoms; said radical being anintegral part of a compound selected from the class consisting of estersand acids; said alcohol containing at least one alkyl hydrocarbonradical having at least eight and not more than thirtytwo carbon atoms.

6. The monohydric aliphatic alcohol ester of an acidic adduct which isan acyclic polybasic alpha-beta unsaturated acid having not over tencarbon atoms, combined at an intermediate point in the carbon atom chainof a non-hydroxylated polyethylenic vegetable fatty acid radical havingeighteen carbon atoms; said radical being an integral part of a compoundselected from the class consisting of esters and acids; said alcoholcontaining at least one alkyl hydrocarbon radical having at least eightand not more than thirtytwo carbon atoms.

7. The monohydric aliphatic alcohol ester of an acidic adduct which isan acyclic polybasic alphabeta unsaturated acid having not over tencarbon atoms, combined at an intermediate point in the carbon atom chainof a polyethylenic vegetable fatty acid radical having eighteen carbonatoms; said radical being an integral part of a compound selected fromthe class consisting of esters and acids; said alcohol containing atleast one alkyl hydrocarbon radical having at least eight and not morethan thirty-twb carbon atoms; at least one long carbon atom chain beingattached to the same carbon atom to which the hydroxyl group isattached.

8. The lauryl alcohol ester of an acidic adduct which is an acyclicpolybasic alpha-beta unsaturated acid having not over ten carbon atoms,combined at an intermediate point in the carbon atom chain of anon-hydroxylated polyethylenlc vegetable fatty acid radical havingeighteen carbon atoms; said radical being an integral part of a compoundselected from the class consisting of esters and acids.

9. The octadecyl alcohol ester of an acidic adduct which is an acyclicpolybasic alpha-beta unsaturated acid having not over ten carbon atoms.combined at an intermediate point in the carbon atom chain of anon-hydroxylated polyethylenic vegetable fatty acid radical havingeighteen carwhich is an acyclic polybasic alpha-beta unsatu- 5 amass 9l0 bon atoms; said radical being an integral part mu m of a compoundselected from the class consisting B one of esters and acids.

The f llowln ferenc at of or i th 10. The cetyl alcohol ester of anacidic adduct 0 g e es 6 rec d m e file of this patent:

rated acid having not over ten carbon atoms, UNITED STATES PATENTScombined at an intermediate point in the carbon atom chain of anon-hydroxylated polyethylenic Number Name Date vegetable fatty acidradical having eighteen car- 2,188,882 Clocker Jan. 30, 1940 bon atoms;said radical being an integral part of to 2,275,843 Clocker Mar. 10,1942 a compound selected from the class consisting 2,312,732 SalathielMar. 2, 1943 of esters and acids.

CHARLES M. BLAIR. JR.

